CN113937341A - Metal zinc secondary battery - Google Patents

Metal zinc secondary battery Download PDF

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CN113937341A
CN113937341A CN202111055633.9A CN202111055633A CN113937341A CN 113937341 A CN113937341 A CN 113937341A CN 202111055633 A CN202111055633 A CN 202111055633A CN 113937341 A CN113937341 A CN 113937341A
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zinc
electrolyte
secondary battery
positive electrode
metal zinc
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王永刚
李智
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Fudan University
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Fudan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/669—Steels
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of electrochemistry, and particularly relates to a metal zinc secondary battery. The metal zinc secondary battery of the invention consists of a positive electrode, a negative electrode and electrolyte; the active material of the positive electrode material is Zn2Fe(PO4)2(ii) a The negative active material is metal zinc; the electrolyte solvent is organic solvent, water or the mixture of the organic solvent and the water, and the solute is organic zinc salt and/or inorganic zinc salt. The cell exhibited good performance in a variety of electrolyte systems. Different from the traditional lithium ion and sodium ion batteries, the zinc battery of the invention can be used for mixed electrolysis of aqueous electrolyte, organic electrolyte, even water and organic solventThe liquid works stably, and the good circulation stability and rate capability are shown. In addition, the electrode material of the battery only contains cheap metal elements such as Fe, Zn and the like, has the advantages of low cost, high safety and environmental friendliness, and can be applied to large-scale energy storage devices.

Description

Metal zinc secondary battery
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a metal zinc secondary battery.
Background
In recent years, various secondary batteries have been rapidly developed, and among them, lithium ion batteries have been widely used in various industries. The growing demand and the poor reserve of lithium resources directly restrict the development of lithium ion batteries. Especially, large-scale energy storage, such as the development of new energy vehicles and smart grids, puts new demands on the development of secondary batteries. The rechargeable zinc ion battery is one of ideal choices for large-scale energy storage due to the advantages of abundant zinc resources, environmental protection, no toxicity, low price, easy obtainment, high chemical stability, high theoretical capacity and the like.
In a secondary battery, an electrolyte is a key component, and physical and chemical properties of the electrolyte have important influences on the service life, electrochemical performance and the like of the battery. At present, commercial secondary batteries mostly work in organic electrolyte, but most of the organic electrolyte has the problems of environmental pollution, potential safety hazards and the like, and the requirement on the purity of an organic solvent is high, so that the production cost is increased. The water system zinc ion battery has the advantages of environmental protection, low cost and high ion conductivity, but the voltage window is narrow (lower than 2V vs2+) Hydrogen evolution/oxygen evolution side reactions are easy to occur, which not only increases the consumption of the electrolyte, but also greatly limits the selection range of the high-voltage anode material. In addition, the zinc dendrite growth, uneven zinc deposition/precipitation, low coulombic efficiency, zinc corrosion, zinc passivation and other problems of the metal zinc cathode in the aqueous electrolyte can reduce the utilization rate and the cycle stability of the zinc cathode.
As described above, the development of an electrolyte having a wide voltage range, low cost, and high ionic conductivity is of great scientific significance and application value in the construction of a high-performance secondary zinc ion battery and its practical process.
Disclosure of Invention
The invention aims to provide a metal zinc secondary battery which can work in a plurality of electrolyte systems and has low cost, long cycle life, high energy density, high and low temperature performance and rate capability.
The invention provides a metal zinc secondary battery, which is based on a metal zinc cathode material and comprises a positive electrode, a negative electrode and electrolyte; wherein the negative electrode active material is metal zinc, and the positive electrode material active material is Zn2Fe(PO4)2(ii) a The electrolyte solvent may be water, an organic solvent, orThe zinc salt is a mixture of water and an organic solvent, and the organic zinc salt and/or inorganic zinc salt is used as a solute. The working principle is that Zn is mainly generated in the charging and discharging process2+Embedding and releasing between the positive electrode and the negative electrode; during charging, Zn2 +The zinc-rich anode is separated from the anode and is deposited to the cathode through electrolyte, and the anode is in a zinc deficiency state; the opposite is true during discharge.
In the invention, the electrochemical performance of the anode material can be improved by nanocrystallization (less than or equal to 1 micron) and surface carbon coating.
In the invention, the methods for nanocrystallization (less than or equal to 1 micron) and surface carbon coating of the cathode material can be sol-gel method, solid phase method, hydrothermal method, microwave method, chemical vapor deposition and the like.
In the invention, the electrolyte solvent is selected from one of water, ethylene glycol, trimethyl phosphate, triethyl phosphate, acetonitrile, N, N-dimethylformamide, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate and propylene carbonate, or a mixture of a plurality of the above. The mixed solvent has the function of adjusting the ionic conductivity, the melting point and other characteristics of the electrolyte.
In the invention, the solute in the electrolyte is selected from one or more of organic zinc salt and inorganic zinc salt, including but not limited to zinc tetrafluoroborate, zinc hexafluorophosphate, zinc trifluoromethanesulfonate, zinc bistrifluoromethanesulfonylimide and zinc sulfate.
In the invention, the concentration range of zinc ions in the electrolyte is 0.01-5 mol/L.
In the invention, the electrolyte also contains one or more of borate, sulfite, sultone, fluoroethylene ester and polyoxyethylene ether as a film forming additive. The additive mainly functions to facilitate the formation of a uniform SEI film, thereby reducing interfacial resistance.
In the invention, the electrolyte also contains one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, isopropylphenyl diphenyl phosphate, cresyl diphenyl phosphate, hexamethoxyphosphazene, tris (2,2, 2-trifluoroethyl) phosphate, bis (2,2, 2-trifluoroethyl) methyl phosphoric acid, (2,2, 2-trifluoroethyl) diethyl ester and hexamethylphosphoramide as an electrolyte flame retardant additive.
In the invention, the positive electrode and the negative electrode are respectively composed of an active substance, a conductive agent, a binder and a current collector.
In the invention, the current collector is one of a titanium mesh, a titanium foil, a stainless steel mesh, a porous stainless steel band, a stainless steel foil, an aluminum mesh, a carbon cloth, a carbon mesh, a carbon felt, a copper mesh and a copper foil, or a composite of a plurality of the titanium mesh, the titanium foil, the stainless steel mesh, the porous stainless steel band, the stainless steel foil, the aluminum mesh, the carbon cloth, the carbon mesh, the carbon felt, the copper mesh and the copper foil.
In the invention, the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, water-soluble rubber, polyvinyl alcohol, polyacrylic acid, sodium alginate and acrylonitrile multipolymer.
In the invention, the conductive additive is one or more of activated carbon, acetylene black, carbon nano tubes, carbon fibers, graphene, graphite, mesoporous carbon and Ketjen black.
The invention provides a zinc ion battery, which takes metal zinc as a negative active material and Zn2Fe(PO4)2As the positive electrode active material, water or an organic solvent and a mixture thereof can be used as the electrolyte. The invention firstly converts Zn into Zn2Fe(PO4)2The zinc-zinc alloy and a metal zinc cathode are prepared into a full battery, high cyclicity and high rate characteristic are realized in various electrolyte environments, and the zinc-zinc alloy can work in a wider temperature range, can be used as one of candidates of an energy storage device, and has a good application prospect.
Detailed Description
The invention is further illustrated by the following specific examples, but is not limited to these examples.
Example 1
Dissolving zinc trifluoromethanesulfonate in water at concentrations of 1, 2 and 3mol/L by using water as a solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P): binder (polyvinylidene fluoride PVDF) 80And (3) mixing the slurry according to the proportion of 10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode plate. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is tested by constant current charge and discharge (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 94mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 87mAh g-1. And the capacity retention rate reaches 91 percent (shown in table 1) after the battery is cycled for 1000 circles at the normal temperature of 25 ℃ and at the current density of 0.5C, and the capacity retention rate reaches 93 percent (shown in table 2) after the battery is cycled for 5000 circles at the current density of 5C.
Example 2
The zinc sulfate is dissolved in water according to the concentration of 1, 2 and 3mol/L by taking water as a solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of an aluminum foil to form the positive electrode sheet. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is subjected to constant current charge and discharge test (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 93mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 88mAh g-1. And the capacity retention rate reaches 88 percent (shown in table 1) after the battery is cycled for 1000 circles at the normal temperature of 25 ℃ and at the current density of 0.5C, and the capacity retention rate reaches 92 percent (shown in table 2) after the battery is cycled for 5000 circles at the current density of 5C.
Example 3
Using acetonitrile as a solvent, and dissolving zinc trifluoromethanesulfonate in acetonitrile according to the concentrations of 0.1, 0.3 and 0.5 mol/L. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode slice. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is tested by constant current charge and discharge (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 89mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 81mAh g-1. And the capacity retention rate reaches 92 percent (shown in table 1) after the battery is cycled for 1000 circles at the normal temperature of 25 ℃ and at the current density of 0.5C, and the capacity retention rate reaches 93 percent (shown in table 2) after the battery is cycled for 5000 circles at the current density of 5C.
Example 4
A mixture of water and acetonitrile (volume ratio is 1:1) is used as a solvent, and zinc trifluoromethanesulfonate is dissolved in the mixture of water and acetonitrile according to the concentration of 1, 2 and 3 mol/L. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode slice. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. Then, the glass fiber is taken as a battery diaphragm, and the assembled zinc ion battery is subjected to constant current charge and discharge test (current density base) on an electrochemical workstationCalculated by the mass of the positive electrode active material), the initial specific capacity of 0.5C is 92mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 84mAh g-1. And the capacity retention rate reaches 85 percent (shown in table 1) after the circuit is cycled for 1200 circles at the normal temperature of 25 ℃ and at the current density of 0.5C, and the capacity retention rate reaches 89 percent (shown in table 2) after the circuit is cycled for 6000 circles at the current density of 5C.
Example 5
Dissolving zinc trifluoromethanesulfonate in N, N-dimethylformamide at concentrations of 0.1, 0.5 and 1mol/L with N, N-dimethylformamide as solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (carbon nanotube): the slurry was mixed with a binder (polyacrylic acid PAA) at a ratio of 80:10:10, and coated on the surface of a titanium foil to form a positive electrode sheet. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is subjected to constant current charge and discharge test (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 88mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 82mAh g-1. And the capacity retention rate reaches 88 percent (shown in table 1) after 1500 cycles at the normal temperature of 25 ℃ and the current density of 0.5C, and the capacity retention rate reaches 92 percent (shown in table 2) after 6000 cycles at the current density of 5C.
Example 6
Dissolving the zinc bis (trifluoromethane sulfonyl) imide into the nitrogen-dimethyl formamide according to the concentration of 0.1, 0.3 and 0.5mol/L by taking the nitrogen-dimethyl formamide as a solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P):and (3) mixing the slurry with a binder (sodium alginate SA) in a ratio of 80:10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode slice. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is subjected to constant current charge and discharge test (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 87mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 81mAh g-1. And the capacity retention rate reaches 92 percent (shown in table 1) after the battery is cycled for 800 circles at the normal temperature of 25 ℃ and at the current density of 0.5C, and the capacity retention rate reaches 91 percent (shown in table 2) after the battery is cycled for 6000 circles at the current density of 5C.
Example 7
The zinc bis (trifluoromethanesulfonyl) imide is dissolved in a mixture of water and acetonitrile at concentrations of 0.1, 0.5 and 1mol/L by using a mixture of water and acetonitrile (volume ratio of 1:1) as a solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode slice. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is subjected to constant current charge and discharge test (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 93mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 86mAh g-1. And after the material is cycled for 2000 circles at the normal temperature of 25 ℃ and the current density of 0.5C, the capacity retention rate reaches 95 percent (see table 1) and the capacity retention rate reaches 5CAfter the current density is circulated for 10000 circles, the capacity retention rate reaches 90 percent (see table 2).
Example 8
The zinc bistrifluoromethanesulfonimide is dissolved in a mixture of water and ethylene glycol at concentrations of 0.1, 0.5 and 1mol/L by taking a mixture of water and ethylene glycol (volume ratio of 1:1) as a solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode slice. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is subjected to constant current charge and discharge test (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 82mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 85mAh g-1. And the capacity retention rate reaches 93 percent (shown in table 1) after 5000 cycles of circulation at the current density of 0.5C and the capacity retention rate reaches 94 percent (shown in table 2) after 5000 cycles of circulation at the current density of 5C at the normal temperature of 25 ℃.
Example 9
Synthesis of carbon-coated nano Zn by sol-gel method2Fe(PO4)2The zinc bistrifluoromethanesulfonylimide is dissolved in a mixture of water and acetonitrile at concentrations of 0.1, 0.5 and 1mol/L using a mixture of water and acetonitrile (volume ratio of 1:1) as a solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode slice. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is tested by constant current charge and discharge (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 97mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 90mAh g-1. And the capacity retention rate reaches 97 percent after the circulation of 2000 circles at the current density of 0.5C at the normal temperature of 25 ℃ (see table 1), and the capacity retention rate reaches 93 percent after the circulation of 10000 circles at the current density of 5C (see table 2).
Example 10
Synthesis of carbon-coated nano Zn by solid phase method and chemical vapor deposition carbon coating mode2Fe(PO4)2The zinc bistrifluoromethanesulfonylimide is dissolved in a mixture of water and acetonitrile at concentrations of 0.1, 0.5 and 1mol/L using a mixture of water and acetonitrile (volume ratio of 1:1) as a solvent. With Zn2Fe(PO4)2As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Zn)2Fe(PO4)2): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the titanium foil to form the positive electrode slice. In this example, the coating amount of the positive electrode was 6mg cm-2. Next, metal zinc is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: and cutting the metal zinc foil into a circular sheet with the diameter of 14mm as a negative electrode plate. And then, assembling the zinc ion button cell by taking glass fiber as a cell diaphragm. The assembled zinc ion battery is tested by constant current charge and discharge (the current density is calculated based on the mass of the positive active material) on an electrochemical workstation, and the initial specific capacity of 0.5C is 99mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the initial specific capacity of 5C was 93mAh g-1. And at the normal temperature of 25 ℃, after circulating for 2000 circles at the current density of 0.5C, the capacity retention rate reaches 95 percent (see table 1), and after circulating for 10000 circles at the current density of 5C, the capacity retention rate is maintainedThe rate reached 95% (see table 2).
Table 1 comparison of cycle performance of zinc ion batteries using different electrolytes
Figure BDA0003254511630000071
Table 2 comparison of cycle performance of zinc ion batteries using different electrolytes
Figure BDA0003254511630000081

Claims (9)

1. A metal zinc secondary battery comprises a positive electrode, a negative electrode and electrolyte; the cathode material is characterized in that the cathode active material is metal zinc, and the anode material active material is Zn2Fe(PO4)2(ii) a The solvent of the electrolyte is water, an organic solvent or a mixture of water and the organic solvent, and the solute is organic zinc salt and/or inorganic zinc salt.
2. The metal zinc secondary battery according to claim 1, wherein the positive electrode material is subjected to nanocrystallization or surface carbon coating treatment to improve electrochemical performance.
3. The metal zinc secondary battery according to claim 1, wherein the organic solvent is one selected from the group consisting of ethylene glycol, trimethyl phosphate, triethyl phosphate, acetonitrile, N-dimethylformamide, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, propylene carbonate, and a mixture of several thereof.
4. The metal zinc secondary battery according to claim 1, wherein the solute in the electrolyte is one or more selected from the group consisting of zinc tetrafluoroborate, zinc hexafluorophosphate, zinc trifluoromethanesulfonate, zinc bistrifluoromethanesulfonylimide, and zinc sulfate.
5. The metal zinc secondary battery according to claim 4, wherein the concentration of zinc ions in the electrolyte is 0.01 to 5 mol/L.
6. The metal zinc secondary battery according to claim 4, wherein the electrolyte further contains one or more of borate, sulfite, sultone, fluoroethylene ester, and polyoxyethylether as a film forming additive.
7. The metal zinc secondary battery according to claim 4, wherein the electrolyte further contains one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, cumyl diphenyl phosphate, cresyl diphenyl phosphate, hexamethoxyphosphazene, tris (2,2, 2-trifluoroethyl) phosphate, bis (2,2, 2-trifluoroethyl) methyl phosphoric acid and (2,2, 2-trifluoroethyl) diethyl ester, hexamethylphosphoramide as an electrolyte flame retardant additive.
8. The metal zinc secondary battery according to any one of claims 1 to 7, wherein the positive electrode and the negative electrode each comprise an active material, a conductive agent, a binder, and a current collector.
9. The metal zinc secondary battery according to claim 8, wherein the current collector is one of a titanium mesh, a titanium foil, a stainless steel mesh, a porous stainless steel belt, a stainless steel foil, an aluminum mesh, a carbon cloth, a carbon mesh, a carbon felt, a copper mesh, a copper foil, or a composite of several thereof; the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, water-soluble rubber, polyvinyl alcohol, polyacrylic acid, sodium alginate and acrylonitrile multipolymer; the conductive additive is one or more of activated carbon, acetylene black, carbon nanotubes, carbon fibers, graphene, graphite, mesoporous carbon and ketjen black.
CN202111055633.9A 2021-09-09 2021-09-09 Metal zinc secondary battery Pending CN113937341A (en)

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